|Budget Amount *help
¥2,100,000 (Direct Cost : ¥2,100,000)
Fiscal Year 1996 : ¥600,000 (Direct Cost : ¥600,000)
Fiscal Year 1995 : ¥1,500,000 (Direct Cost : ¥1,500,000)
1.A novel cobalt (III) complex containing a dimerized 6-amino-2-thiouracilato ligand was synthesized and characterized by X-ray crystal structure. The formation mechanism of such homo-assembly was investigated in detail. These results were reported in J.Chem.Soc., Dalton Trans., (16), 2627 (1995).
2.The assemblies of hetero ligands were found in the mixed system of 4,6-diamino-2-thiouracil and thiobarbituric acid. The complexes were characterized by NMR spectroscopy and X-ray crystal structure. The results were communicated in Chem.Lett., (8), 673 (1995).
3.Seven bis (thane-1,2-diamine) cobalt (III) complexes containing five purinethiones were thermally or photochemically prepared. The crystal structure of [Co (put) (en) _2] Cl・2H_2O shows that the put ligand coordinates through S^6 and N^7 forming a five-membered chelate ring. The other purine-6-thione ligands all adopt this mode rather than the four-membered one of N^1/S^6. Carbon-13 NMR spectroscopy is very useful for the assignment of the above linkage isomers. These results were reported in J.Chem.Soc., Dalton Trans., (2), 305 (1996).
4.Nine bis (2,2'-bipyridine) ruthenium (II) complexes containing pyrimidine-2-thione and its related ligands were prepared. Two linkage isomers, adjacent and remote, exist for all the complexes with unsymmetrical ligands except for apymt. The crystal structure of [Ru (mpymt) (bipy) 2] CIO4 indicates that the mpymt ligand coordinates through the S2/N3 donors and the complex adopts an adjacent linkage form where the 4-methyl group is just on one of the bipy chelate rings irrespective of steric hindrance. It turned out that CH/pi attractive interaction between the 4-or 6-alkyl group of thione ligand and pi-system of bipy affects the isomeric ratios in a striking manner. These results were reported in J.Chem.Soc., Dalton Trans., (13), 2851 (1996).